The proposed work outlines an investigation into the design of processes used to form congested, multiply substituted bonds by taking advantage of a functional group's reversal of polarity. The reactions under investigation will rely on the use of catalytic amounts of a chiral source. Once a foundation for the key reactivity has been laid, we will turn our attention of applying this research to the rapid and stereoselective synthesis of a number of biologically active targets. Azaspirene is a novel angiogenesis inhibitor, a potential target for anti-cancer agents. Asparagamine A is a potent nicotinic acetylcholine receptor antagonist. Its stereochemically dense, polycyclic structure provides an incentive for us to develop a better, more efficient approach to these molecules. Lastly, we hope to develop a general approach to controlling absolute stereochemistry in a subfield of reactions that utilize radicals to form new bonds. Accomplishing this feat would open new vistas in complex molecule assembly that could take advantage of the ability of radicals to sequence multiple chemical transformations in a single step.